Supported nickel catalysts having high nickel loading and high metal dispersion and methods of making same
View Patent ↗Supported nickel catalyst having high nickel loading and dispersion are manufactured using a dispersing agent. The dispersing agent molecules include at least one functional group that bonds with the nickel atoms and influences nanoparticle formation. The support material is loaded with at least about 5% nickel, more preferably at least about 8%, and most preferably at least about 12% by weight of the total catalyst. Catalysts manufactured using the organic dispersing agents and loaded with the foregoing amounts of nickel have metal dispersions greater than about 5% as measured by hydrogen adsorption, more preferably greater than about 10%, and most preferably greater than about 15%.
1. A supported nickel nanocatalyst, comprising,
a catalyst support material;
a plurality of catalyst nanoparticles comprised of nickel dispersed on the support material; and
a plurality of dispersing agent molecules bonded to the plurality of nanoparticles and optionally to the support material,
wherein the catalyst nanoparticles provide a nickel loading on the support material of at least about 5% by weight and a metal dispersion of at least about 5%, as measured by hydrogen adsorption.
2. A supported nickel nanocatalyst as in claim 1 , wherein the nickel loading is greater than about 8% by weight.
3. A supported nickel nanocatalyst as in claim 1 , wherein the nickel loading is greater than about 12% by weight.
4. A supported nickel nanocatalyst as in claim 1 , wherein the metal dispersion is greater than about 10%, as measured by hydrogen adsorption.
5. A supported nickel nanocatalyst as in claim 1 , wherein the metal dispersion is greater than about 15%, as measured by hydrogen adsorption.
6. A supported nickel nanocatalyst as in claim 1 , in which the dispersing agent molecules are bonded to the catalyst nanoparticles by at least one functional group selected from the group consisting of a hydroxyl, a carboxyl, a carbonyl, an amine, an amide, a nitrile, a nitrogen with a free lone pair of electrons, an amino acid, a thiol, a sulfonic acid, a sulfonyl halide, and an acyl halide.
7. A supported nickel nanocatalyst as in claim 1 , in which the support material comprises one or more of carbon black, graphite, silica, alumina, zeolite, metal oxide, or polymer.
8. A supported nickel nanocatalyst as in claim 1 , in which the catalyst nanoparticles further comprise molybdenum.
9. A method for manufacturing a supported nickel-containing nanocatalyst, comprising:
(i) providing a catalyst support material;
(ii) providing a solution comprised of nickel atoms;
(iii) providing a solution comprised of dispersing agent molecules, each having at least one functional group capable of bonding with the nickel atoms;
(iv) reacting the nickel atoms with the dispersing agent molecules and causing or allowing the nickel atoms to form nickel-containing catalyst nanoparticles; and
(v) loading the nickel atoms and/or catalyst nanoparticles on the catalyst support material in an amount so as to provide a nickel loading of at least about 5% by weight of the catalyst, exclusive of solvent.
10. A method as in claim 9 , in which the reaction of the nickel atoms with the dispersing agent is carried out in a solution having a pH greater than 7.0.
11. A method as in claim 9 , in which (iv) is performed before step (v).
12. A method as in claim 9 , in which (v) is performed before step (iv).
13. A method as in claim 9 , in which the dispersing agent molecules comprise at least one type of functional groups capable of bonding to the support material.
14. A method as in claim 13 , in which the functional group capable of bonding to the support comprises at least one member selected from the group consisting of a hydroxyl, a carboxyl, a carbonyl, an amine, an amide, a nitrile, a nitrogen with a free lone pair of electrons, an amino acid, a thiol, a sulfonic acid, a sulfonyl halide, and an acyl halide.
15. A method as in claim 9 , in which the support material comprises one or more of carbon black, graphite, silica, alumina, zeolite, metal oxide, or polymer.
16. A method as in claim 9 , in which the solution of nickel atoms and the solution of dispersing agent molecules comprise a solvent selected from the group consisting of water, methanol, ethanol, n-propanol, isopropyl alcohol, acetonitrile, acetone, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, methylene chloride, and combinations thereof.
17. A method as in claim 9 , in which the organic dispersing agent comprises at least one member selected from the group consisting of adipic acid, oxalic acid, malic acid, malonic acid, maleic acid, succinic acid, glycolic acid, lactic acid, glucose, citric acid, EDTA, pectins, cellulose, ethanolamine, mercaptoethanol, 2-mercaptoacetate, glycine, sulfobenzyl alcohol, sulfobenzoic acid, sulfobenzyl thiol, sulfobenzyl amine, polyacrylates, polyvinylbenzoates, polyvinyl sulfate, polyvinyl sulfonates, polybisphenol carbonates, polybenzimidizoles, polypyridine, and sulfonated polyethylene terephthalate.
18. A method as in claim 9 , wherein the catalyst is dried, calcined, or used in a catalytic reaction at a temperature greater than 100° C.
19. A dispersed supported nickel nanocatalyst manufactured according the method of claim 9 .
20. A method for manufacturing a supported nickel nanocatalyst, comprising:
(i) providing a catalyst support material;
(ii) providing a plurality of nickel atoms;
(iii) providing a plurality of organic dispersing agent molecules, each having at least one functional group capable of bonding with a nickel atom;
(iv) forming a plurality of nickel complexes by reacting the nickel atoms with an inorganic ligand;
(v) reacting the nickel complexes with the dispersing agent molecules in a solution having a pH greater than 7.0 to bond the dispersing agent to the nickel atoms;
(vi) causing or allowing the nickel atoms bonded to the dispersing agent to form nickel-containing catalyst nanoparticles; and
(vii) loading the nickel atoms and/or catalyst nanoparticles on the catalyst support material in an amount so as to provide a nickel loading of at least about 5% by weight of the catalyst, exclusive of solvent.
21. A method as in claim 20 , further comprising calcining the support material prior to loading the nickel atoms or nickel nanoparticles thereon.
22. A method as in claim 20 , in which the inorganic ligand is selected from the group consisting of ammonium, hydroxide, chloride, nitrate, sulfate, carbonate, and combinations thereof.
23. A method as in claim 20 , in which the inorganic ligand is provided using a base.
24. A method as in claim 23 , wherein the base comprises a solution of ammonium carbonate and ammonium hydroxide.
25. A method as in claim 24 , wherein the ratio of ammonium carbonate to ammonium hydroxide is greater than about 2:1.
26. A method as in claim 24 , wherein the ratio of ammonium carbonate to ammonium hydroxide is greater than about 3:1.
27. A method as in claim 20 , in which the pH of the solution is greater than about 7.5.
28. A method as in claim 20 in which the pH of the solution is greater than about 8.0.
29. A method as in claim 20 , in which the at least one functional group is selected from the group consisting of a hydroxyl, a carboxyl, a carbonyl, an amine, an amide, a nitrile, a nitrogen with a free lone pair of electrons, an amino acid, a thiol, a sulfonic acid, a sulfonyl halide, and an acyl halide.
30. A method as in claim 20 , in which the nickel is loaded on the catalyst support in an amount greater than 12% by weight of the final catalyst.